基于梳状结构的复杂交联聚己内酯的合成及形状记忆行为  

Synthesis and Shape Memory Behavior of Complex Cross-Linked Polycaprolactone Based on Comb Structure

作　　者：王怡莹 冷雪菲[1] 张稳稳 高梦云 李杨[1] Yiying Wang;Xuefei Leng;Wenwen Zhang;Mengyun Gao;Yang Li(State Key Laboratory of Fine Chemicals,Key Laboratory of Polymer Science and Engineeringof Liaoning Province,Department of Polymer Science and Engineering,School of Chemical Engineering,Dalian University of Technology,Dalian 116024,China)

机构地区：[1]大连理工大学精细化工国家重点实验室,辽宁省高分子科学与工程重点实验室,大连理工大学化工学院高分子材料系,辽宁大连116024

出　　处：《高分子材料科学与工程》2021年第4期158-165,共8页Polymer Materials Science & Engineering

基　　金：国家自然科学基金资助项目(51803019)。

摘　　要：以正丁基锂为引发剂,通过活性阴离子聚合得到窄分布的聚丁二烯,然后通过环氧化和羟基化反应得到多羟基聚丁二烯。并以多羟基聚丁二烯作为大分子引发剂,通过开环聚合方法合成了梳状聚己内酯(gPCL),通过核磁共振波谱和凝胶渗透色谱测定结构信息,证明得到了分子量分布窄(PDI<1.18)的具有接枝结构的梳状聚己内酯。通过合成的梳状聚己内酯与六甲基二异氰酸酯(HDI)进行交联反应合成了一系列基于梳状结构的复杂交联聚己内酯(C-gPCL)。利用傅里叶变换红外光谱、差示扫描量热仪、广角X射线衍射、动态力学热分析仪、万能拉伸机等测试方法对获得的交联聚合物的性能进行了表征并对交联聚合物的形状记忆行为进行了分析。交联后的聚合物具有热致形状记忆效应,初始形变量为50%时,形状固定率可达99.6%,12 s即可回复形状且形状回复率可达98.8%;高支化结构的引入使得材料形状记忆效应更稳定,经过5次形状记忆过程循环后(单次形变量为50%),形状固定率仍达92.2%,形状回复率达93.6%。By using hydroxylated polybutadiene as macromolecular initiator,graft polycaprolactone was synthesized by ring-opening polymerization.The graft structure was determined by~1H-NMR and GPC.A series of crosslinked polymers were synthesized by crosslinking gPCL with hexamethyldiisocyanate(HDI).FT-IR,DSC,WAXD,dynamic thermo-mechanical analysis(DMA),universal stretching machine and other test methods were used to characterize and analyze the microstructure of the crosslinked polymer.The crosslinked polymer has a thermogenic shape memory effect.When the initial shape variable is 50%,the shape fixation rate can reach 99.6%.The shape can be recovered after 12 s with a recovery rate of 98.8%.The introduction of high graft structure makes the shape memory effect of materials more stable.After 5 cycles of shape memory(50%for single shape),the shape fixation rate is still 92.2%and the shape recovery rate is 93.6%.

关 键 词：梳状聚合物 交联网状 聚己内酯 形状记忆性能 

分 类 号：TQ323.4[化学工程—合成树脂塑料工业]